N-(3-Chloro­phen­yl)-2,4-dimethyl­benzene­sulfonamide

K Shakuntala; Sabine Foro; B Thimme Gowda

doi:10.1107/S1600536811029400

. 2011 Jul 30;67(Pt 8):o2178. doi: 10.1107/S1600536811029400

N-(3-Chlorophenyl)-2,4-dimethylbenzenesulfonamide

K Shakuntala ^a, Sabine Foro ^b, B Thimme Gowda ^a,^*

PMCID: PMC3213612 PMID: 22091189

Abstract

In the molecule of the title compound, C₁₄H₁₄ClNO₂S, the N—H bond is in a syn position with respect to the meta-Cl atom in the aniline ring. The molecule is twisted about the N—S bond with a C—SO₂—NH—C torsion angle of 44.55 (17)°. The two aromatic rings are inclined relative to each other by 66.2 (1)°. In the crystal, N—H⋯O hydrogen bonds link the molecules into infinite chains parallel to the b axis.

Related literature

For hydrogen bonding modes of sulfonamides, see: Adsmond & Grant (2001 ▶). For studies on the effects of substituents on the structures and other aspects of N-(aryl)-amides, see: Arjunan et al. (2004 ▶); Gowda et al. (1999 ▶), on N-(aryl)methanesulfonamides, see: Gowda et al. (2007 ▶) and on N-(aryl)arylsulfonamides, see: Gelbrich et al. (2007 ▶); Gowda et al. (2010 ▶); Perlovich et al. (2006 ▶). For the preparation of the title compound, See: Savitha & Gowda (2006 ▶)

Experimental

Crystal data

C₁₄H₁₄ClNO₂S
M _r = 295.77
Monoclinic,
a = 9.0385 (7) Å
b = 9.7830 (7) Å
c = 15.897 (1) Å
β = 97.284 (7)°
V = 1394.33 (17) Å³
Z = 4
Mo Kα radiation
μ = 0.42 mm⁻¹
T = 293 K
0.44 × 0.40 × 0.32 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.837, T _max = 0.877
5245 measured reflections
2841 independent reflections
2438 reflections with I > 2σ(I)
R _int = 0.009

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.103
S = 1.06
2841 reflections
177 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.36 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811029400/bt5582sup1.cif

e-67-o2178-sup1.cif^{(17.5KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811029400/bt5582Isup2.hkl

e-67-o2178-Isup2.hkl^{(139.5KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811029400/bt5582Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1ⁱ	0.84 (2)	2.32 (2)	3.117 (2)	158 (2)

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Symmetry code: (i) Inline graphic .

Acknowledgments

KS thanks the University Grants Commission, Government of India, New Delhi, for the award of a research fellowship under its faculty improvement program.

supplementary crystallographic information

Comment

The amide and sulfonamide moieties are the constituents of many biologically important compounds. The hydrogen bonding preferences of sulfonamides have been investigated (Adsmond & Grant, 2001). As part of our work on the substituent effects on the structures and other aspects of N-(aryl)-amides (Arjunan et al., 2004; Gowda et al., 1999), N-(aryl)-methanesulfonamides (Gowda et al., 2007) and N-(aryl)-arylsulfonamides (Gowda et al., 2010), in the present work, the crystal structure of N-(3-chlorophenyl)-2,4-dimethylbenzene- sulfonamide (I) has been determined (Fig. 1). The conformation of the N—C bond in the C—SO₂—NH—C segment has gauche torsions with respect to the S═O bonds. The molecule is bent at the S atom with the C1—SO₂—NH—C7 torsion angle of 44.6 (2)°, compared to the values of -54.9 (2)° in N-(2-chlorophenyl)-2,4-dimethylbenzenesulfonamide (II) (Gowda et al., 2010). Further, the conformation of the N—H bond in (I) is syn to the meta-chloro group in the anilino ring.

The two benzene rings in (I) are tilted relative to each other by 75.7 (1)°, compared to the value of 66.2 (1)° (II). The other bond parameters in (I) are similar to those observed in (II) and other aryl sulfonamides (Perlovich et al., 2006; Gelbrich et al., 2007).

The crystal packing of molecules in (I) via N—H···O(S) hydrogen bonds (Table 1) is shown in Fig.2.

Experimental

The solution of 1,3-xylene (1,3-dimethylbenzene) (10 ml) in chloroform (40 ml) was treated dropwise with chlorosulfonic acid (25 ml) at 0 ° C. After the initial evolution of hydrogen chloride subsided, the reaction mixture was brought to room temperature and poured into crushed ice in a beaker. The chloroform layer was separated, washed with cold water and allowed to evaporate slowly. The residual 2,4-dimethylbenzenesulfonylchloride was treated with 3-chloroaniline in the stoichiometric ratio and boiled for ten minutes. The reaction mixture was then cooled to room temperature and added to ice cold water (100 cc). The resultant solid N-(3-chlorophenyl)-2,4-dimethylbenzenesulfonamide was filtered under suction and washed thoroughly with cold water. It was then recrystallized to constant melting point from dilute ethanol. The purity of the compound was checked and characterized by recording its infrared and NMR spectra (Savitha & Gowda, 2006).

The prism like colourless single crystals used in X-ray diffraction studies were grown in ethanolic solution by a slow evaporation at room temperature.